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[Co 5 Tp* 4 (Me 2 bta) 6 ]: A Highly Symmetrical Pentanuclear Kuratowski Complex Featuring Tris(pyrazolyl)borate and Benzotriazolate Ligands

2016; American Chemical Society; Volume: 55; Issue: 3 Linguagem: Inglês

10.1021/acs.inorgchem.5b01982

1520-510X

Tamas W. Werner, S. Reschke, Hana Bunzen, Hans‐Albrecht Krug von Nidda, J. Deisenhofer, A. Loidl, Dirk Volkmer,

Organometallic Complex Synthesis and Catalysis

The pentanuclear Co(II) complex [Co5Tp*4(Me2bta)6] containing N-donor ligands (5,6-dimethyl benzotriazolate; Me2bta6) and N-donor capping ligands (tris(3,5-dimethyl-1-pyrazolyl)borate; Tp*) was prepared by a simple and efficient ligand exchange reaction from [Co5Cl4(Me2bta)6] and tetra-n-butyl ammonium tris(3,5-dimethyl-1-pyrazolyl)borate. Compared to the precursor complex [Co5Cl4(Me2bta)6], which contains one Co(II) ion in octahedral and four Co(II) ions in tetrahedral coordination geometry, the title compound features all five Co(II) ions in an octahedral coordination environment while keeping a high complex symmetry. This results in modified properties including improved solubility and distinct magnetic behavior as compared to the precursor complex. The molecular structure and phase purity of the compound was verified by XRPD, UV–vis, ESI-MS, IR, and NMR measurements. Thermal stability of the compound was determined via TGA. The magnetic properties of here reported novel complex [Co5Tp*4(Me2bta)6] as well as its precursor [Co5Cl4(Me2bta)6] were examined in detail via ESR and SQUID measurements, which indicated weak anti-ferromagnetic exchange interactions between high-spin Co(II) centers at T < 20 and 50 K, respectively.